[go: up one dir, main page]

EP0897947B2 - Pellicule en polyester contenant des cellules infimes - Google Patents

Pellicule en polyester contenant des cellules infimes Download PDF

Info

Publication number
EP0897947B2
EP0897947B2 EP98114927A EP98114927A EP0897947B2 EP 0897947 B2 EP0897947 B2 EP 0897947B2 EP 98114927 A EP98114927 A EP 98114927A EP 98114927 A EP98114927 A EP 98114927A EP 0897947 B2 EP0897947 B2 EP 0897947B2
Authority
EP
European Patent Office
Prior art keywords
polyester film
fine cell
gloss
containing polyester
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98114927A
Other languages
German (de)
English (en)
Other versions
EP0897947A3 (fr
EP0897947A2 (fr
EP0897947B1 (fr
Inventor
Takashi c/o Diafoil Hoechst Company Ltd. Hibiya
Takatoshi c/o Diafoil Hoechst Company Ltd. Miki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Polyester Film Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27476825&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0897947(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from JP21740897A external-priority patent/JP3982774B2/ja
Priority claimed from JP9217409A external-priority patent/JPH1160766A/ja
Priority claimed from JP9294034A external-priority patent/JPH11130887A/ja
Priority claimed from JP9331511A external-priority patent/JPH11157037A/ja
Application filed by Mitsubishi Polyester Film Corp filed Critical Mitsubishi Polyester Film Corp
Publication of EP0897947A2 publication Critical patent/EP0897947A2/fr
Publication of EP0897947A3 publication Critical patent/EP0897947A3/fr
Publication of EP0897947B1 publication Critical patent/EP0897947B1/fr
Application granted granted Critical
Publication of EP0897947B2 publication Critical patent/EP0897947B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a fine cell-containing polyester film, and more particularly, to a fine cell-containing polyester film which is excellent in gloss, printability, transport property and/or flexibility; image-receiving papers suitable for a video printer, which are excellent in image-receiving property and transport property, and has a good printability; and release papers suitable for seal print, which are excellent in adhesion to a coating layer applied thereon.
  • Polyester films have widely used as industrial materials because the films have various well-balanced properties and are excellent in cost performance.
  • fine cell-containing polyester films which are produced, as light-weight white opaque films having a cushioning, property, by blending polyester with a thermoplastic resin immiscible therewith and molding the resultant blend into a film shape, have been applied, for example, to synthetic papers such as mounts for seal print, base films of magnetic cards or the like.
  • the fine cell-containing polyester films have been advantageously used as image-receiving papers or mounts (release papers) for products such as seal print or the like, because of an excellent cushioning property thereof.
  • the fine cell-containing polyester films have been used as image-receiving papers having the size of post card on which video images are directly printed.
  • opposite surfaces of the image receiving paper have different properties from each other. That is, the front surface of the image-receiving paper on which images' are to be printed, is required to have a high gloss (low surface roughness) in order to receive precise print images thereon.
  • the opposite (rear) surface of the image-receiving paper is required to have a low gloss (high surface roughness) in order to impart a high transport property thereto.
  • the fine cell-containing polyester films have been produced by melt-kneading polyester and a thermoplastic resin immiscible therewith in an extruder, extruding the resultant melted material through an extrusion die on a casting roll to cool and form an amorphous sheet, followed by successively subjecting the obtained sheetto longitudinal stretching treatment, transverse stretching treatment and heat treatment.
  • the melted material composed of polyester and the immiscible thermoplastic resin is extruded on the casting roll and contacted with a surface thereof.
  • a surface of the resultant sheet where the sheet is contacted with the casting roll (cast surface).
  • the cast surface of the resultant oriented film shows a larger gloss than that of the air-side surface thereof. Accordingly, in order to eliminate the double transport, it is suitable that the cast surface and air-side surface of the film are used as a printing surface and a back feed surface, respectively.
  • the amount of the immiscible thermoplastic resin deposited on the surface of the casting roll is considerably increased, the deposited immiscible thermoplastic resin is transferred onto a cast surface of respective films subsequently produced, so that uneven patterns tend to be formed thereon, thereby causing severe damage to quality of the products when used for printing.
  • the gloss of the fine cell-containing polyester film may be increased by laminating a polyethylene terephthalate homopolymer layer containing no fine cells on the fine cell-containing polyester film.
  • a polyethylene terephthalate homopolymer layer containing no fine cells on the fine cell-containing polyester film in order to impart a desired gloss to the film, it is necessary to increase the thickness of the homopolymer layer.
  • Such an increased thickness of the homopolymer layer causes problems that the flexibility of the film is lost as a whole and the resultant prints are deteriorated in printing density.
  • DE 195 40 277 A1 discloses a polyester film having fine voids comprising a polymer blend containing a polyester resin and a thermoplastic resin incompatible with said polyester resin, and having a specific gravity of 0.6 - 1.3 as well as a certain birefringence value, said polyester film being suitable for substrate materials.
  • the obtained fine cell-containing polyester film is excellent in gloss, printability, transport property, heat resistance and/or surface smoothness, has an appropriate flexibility and is useful as a base film of image-receiving papers for a video printer and release papers for print seal.
  • the present invention has been attained on the basis of the finding.
  • a fine cell-containing polyester film according to claim 1 the higher-gloss surface of the polyester film having a gloss G C of not less than 33 %, preferably 33 to 47%, and the lower-gloss surface of said polyester film having a gloss G A of 25 ⁇ 7%, preferably 20 to 30 %.
  • a fine cell-containing polyester film according to claim 1 the higher-gloss surface whose the gloss of is not less than 25 %, having a surface roughness Ra of 0.06 to 0.25 ⁇ m, preferably 0.08 to 0.20 ⁇ m.
  • a fine cell-containing polyester film according to claim 1 and the thermoplastic resin immiscible with the polyester containing a nonionic surfactant.
  • an image-receiving paper for a video printer comprising:
  • an image-receiving paper for a video printer comprising:
  • a release paper for a print seal comprising a fine cell-containing polyester film according to claim 1, the higher-gloss surface of the polyester film having a gloss G C of not less than 33 %, and the lower-gloss surface of said polyester film having a gloss G A of 25 ⁇ 7 %.
  • Polyesters constituting the fine cell-containing polyester film according to the present invention may be those produced from, for example, an aromatic dicarboxylic acid or an ester thereof' and a glycol is primary starting materials, and having repeating units comprising not less than 80 % of ethylene terephthalate units or ethylene-2, 6-naphthalate units. Further, the polyesters may contain the third components unless the content thereof departs from the afore-mentioned range.
  • Examples of the suitable aromatic dicarboxylic acids used for the production of the polyester may include terephthalic acid, 2, 6-naphthalene dicarboxylic acid, isophthalic acid, phthalic acid, adipic acid, sebacic acid, oxycarboxylic acid such as p-oxyethoxy-benzoic acid, or the like. These aromatic dicarboxylic acids can be used singly or in the form of a mixture of any two or more thereof.
  • Examples of the suitable glycols used for the production of the polyester may include ethylene glycol, diethylene glycol, propylene glycol, butane diol, 1, 4-cyclohexane dimethanol, neopentyl glycol or the like. These glycols can be used singly or in the' form of a mixture of any two or more thereof.
  • the fine cell-containing polyester film there may be preferably used a method of stretching a polyester composition containing a thermoplastic resin immiscible with polyester, in at least one direction.
  • the content (An) of the polyester-immiscible thermoplastic resin is usually 3 to 30 % by weight, preferably 5.0 to 25 % by weight, more preferably 8.0 to 25 % by weight, still more preferably 10 to 20 % by weight based on the total weight of the polyester and the immiscible thermoplastic resin.
  • the content (An) thereof is less than 3.0 % by weight, the amount of fine cells formed in the film becomes too small, so that the resultant film cannot exhibit a sufficiently reduced weight and a good cushioning property which are features of fine cell-containing polyester films.
  • thermoplastic resins immiscible with polyester may'include polyolefins such as polyethylene, polypropylene, polymethyl pentene or polymethyl butene, polystyrene, polycarbonates, polyphenyl sulfides, liquid crystal polyesters or the like.
  • polyolefins such as polyethylene, polypropylene, polymethyl pentene or polymethyl butene, polystyrene, polycarbonates, polyphenyl sulfides, liquid crystal polyesters or the like.
  • polypropylene, polymethyl pentene and polystyrene are preferred, and polypropylene is more preferred.
  • the above-mentioned preferred polypropylenes are crystalline polypropylene homopolymers having usually not less than 95 mol %, preferably not less than 98 mol % of. propylene units.
  • amorphous polypropylene is used as the immiscible thermoplastic resin
  • the bleed-out of the polypropylene is caused on a surface of an unoriented sheet during the production of the film, so that a cooling drum, a stretching roll or the like is apt to be soiled therewith.
  • the polypropylene is copolymerized with - more than 5 mol % of other units than propylene, e.g., ethylene units, there may be a tendency that the amount of the fine cells formed in the polyester is insufficient.
  • the melt flow index (MFI) of the afore-mentioned polypropylene is usually in the range of 0.5 to 30 g/10 min, preferably 1.0 to 15 g/10 min.
  • MFI melt flow index
  • the MFI of the polypropylene is less than 0.5 g/10 min, the size of the cells formed may become too large, so that breaking or rupture of the resultant film is likely to occur upon stretching thereof.
  • the MFI of the polypropylene is more than 30 g/10 min, the uniformity in density of the film may tend to be deteriorated with the passage of time, resulting in deteriorated productivity in the production line of the film.
  • the polyester-immiscible thermoplastic resin contains (e.g., by kneading therewith) as a lubricant lauramide, stearamide, oleamide, erucamide, n-oleyl palmitamide, ethylene bis-stearamide.
  • amides of unsaturated higher fatty acids having not less than 10 carbon atoms such as oleamide or erucamide are preferred because these amides can exhibit a high lubricating effect.
  • the content of the above-mentioned lubricant in the polyester-immiscible thermoplastic resin is usually 0.005 to 2.0 % by weight, preferably 0.01 to 1.0 % by weight based on the total weight of the lubricant and the polyester-immiscible thermoplastic resin.
  • the content of the lubricant is less than 0.005 % by weight, the effect of preventing the thermoplastic resin from being separated from polyester when the film is cooled on the casting roll, may be deteriorated.
  • the content of the lubricant is more than 2.0 % by weight, the effect of preventing the separation of the thermoplastic resin is already saturated and brightness of the resultant film is deteriorated, so that the quality of the resultant film may tend to be adversely affected.
  • a nonionic surfactant be contained (e.g., incorporated by kneading) in the thermoplastic resin immiscible with polyester.
  • the above-mentioned nonionic surfactant means a compound capable of remarkably modifying the property of an interface between different molten polymer blends, i. e., exhibiting such an effect of increasing a compatibility of polyester with the immiscible thermoplastic resin at an interface therebetween.
  • the nonionic surfactants may include polyalkylene glycol-based surfactants, polyhydric alcohol-based surfactants, silicone-based surfactants or the like. Among them, the silicone-based surfactants are preferred. Specifically, organopolysiloxane-polyoxyalkylene copolymers, alkenylsiloxanes having polyoxyalkylene moieties as side chains or the like are more preferred because these compounds have a high surface activity.
  • the content of the nonionic surfactant in the thermoplastic resin immiscible with polyester is usually 0.01 to 10 % by weight, preferably 0.2 to 5.0 % by weight based on the total weight of the nonionic surfactant and the polyester-immiscible thermoplastic resin.
  • the content of the surfactant is less than 0.01 % by weight, there may be a tendency that the effect of inhibiting the falling-off or separation of the thermoplastic resin from polyester on the casting roll, is reduced.
  • the content of the surfactant is more than 10 % by weight, the effect of inhibiting the falling-off or separation of the thermoplastic resin from polyester is already saturated, and there may be a tendency that the resultant film undergoes deteriorated quality such as low brightness.
  • the gloss of the fine cell-containing polyester film according to the present invention can be expressed by a value measured by Method 3 of JIS Z 8741-1983 (60° gloss). In accordance with the present invention, it is desired that the difference in gloss between the opposite surfaces of the polyester film is not less than 3 %, and the higher-gloss surface of the polyester film has a gloss of not less than 25 %.
  • the difference in gloss between the opposite surfaces of the polyester film is less than 3 %, surface properties required for the image-receiving surface and the' rear surface (which contributes to transport property of the film) cannot be satisfied.
  • the higher-gloss surface of the polyester film is used as an image-receiving surface.
  • the image-receiving surface of the polyester film has a low gloss similar to that of the rear surface thereof, the printed image on the image-receiving surface is unsatisfactory in definition or clarity.
  • the difference in gloss between the opposite surfaces of the polyester film is preferably not less than 5 %, more preferably not less than 10 %.
  • the higher-gloss surface of the polyester film has a gloss of preferably not less than 30 %, more preferably not less than 33 %, still more preferably not less than 35 %.
  • the upper limit of the gloss of the higher-gloss surface of the polyester film is preferably 80 % for the non-laminated polyester film according to the invention.
  • the gloss (G C ) of the higher-gloss surface of the polyester film is preferably 40 ⁇ 7 %, more preferably 40 ⁇ 5 %.
  • the gloss (G A ) of the opposite surface (lower-gloss surface) of the polyester film is preferably 25 ⁇ 7 %, more preferably 25 ⁇ 5 %, still more preferably 25 ⁇ 3 %.
  • the gloss (G A ) of the lower-gloss surface is less than 18 %, the rear surface of the polyester film may become considerably rough, resulting in damaging a favorable touch when used as products such as seal prints.
  • the polyesters as a raw material of the fine cell-containing polyester film according to the present invention preferably have an intrinsic viscosity (IV A ) of 0.45 to 0.70 at the film-forming stage.
  • IV A intrinsic viscosity
  • the breaking of the polyester film may tend to be caused upon the film formation, so that fine cells having uneven sizes may be formed in the film and it may become difficult to control a density of the film.
  • the intrinsic viscosity (IV A ) is more than 0.70, there may be tendency that the amount of fine cells formed in the film may tend to be reduced.
  • the density of the fine cell-containing polyester film according to the present invention is usually 0.70 to 1.30 g/cm 3 , preferably 0.80 to 1.25 g/cm 3 , more preferably 0.90 to 1.20 g/cm 3 .
  • the resultant film may tend to be deteriorated in cushioning property which is one of features of the fine cell-containing polyester film according to the present invention.
  • the density of the polyester film is less than 0.70 g/cm 3 , the resultant polyester film may be insufficient in mechanical strength and thermal stability, resulting in adversely affecting a quality thereof and inhibiting a continuous production thereof.
  • the surface roughness (Ra) of the lower-gloss surface of the fine cell-containing polyester film according to the present invention is usually not less than 0.08 ⁇ m, preferably 0.08 to 0.40 ⁇ m, more preferably 0.08 to 0.25 ⁇ m, still more preferably 0.10 to 0.20 ⁇ m.
  • the surface roughness (Ra) is less than 0.08 ⁇ m, there may be a tendency that paper feeling peculiar to fine cell-containing polyester films is deteriorated.
  • the polyester film according to the present invention can exhibit not only a good brightness but also a high optical density from the standpoint of imparting a high-grade appearance to these products.
  • titanium dioxide, barium sulfate or other white pigments may be added thereto.
  • a fluorescent brightening agent may be added to the film.
  • any two or more of these white pigments may be added to the polyester film.
  • the content of the white pigment is preferably 0.5 to 20 % by weight, more preferably 1.0 to 15 % by weight based on the total weight of the raw materials of the film.
  • the content of the fluorescent brightening agent is preferably 0 to 0.30 % by weight based on the total weight of the raw materials of the film.
  • the optical density of the polyester film according to the present invention is usually not less than 0.3, preferably not less than 0.5.
  • the optical density is less than 0.3, there may be a tendency that the film is deteriorated in applicability to image-receiving papers or seal prints.
  • the brightness of the polyester film according to the present invention can be expressed by a W value measured by Method C of JIS L 1015-1981.
  • the W value of the polyester film according to the present invention is usually not less than 70, preferably not less than 80. When the W value is less than 70, the film may be deteriorated in tint thereof, thereby failing to impart a high-grade appearance to the polyester film when used as image-receiving papers or seal prints.
  • additives such as anti-oxidizing agents, heat stabilizers, anti-static agents, dyes, pigments, surfactants or the like may be blended in polyester and/or polypropylene, if required.
  • the polyester film according to the present invention may be provided on opposite surfaces thereof with a silicone coat (release layer), a back coat layer (rear surface-coating layer) or the like.
  • various primer layers may be formed on any of the opposite surfaces of the polyester film.
  • the primer layer composed of water-soluble or water-dispersible polyester-based resins and water-soluble or water-dispersible polyurethane-based resins may be applied either during or after production of the film.
  • polyester-based resins used for the production of the primer layer there may be used any known polyesters as described in Japanese Patent Publication (KOKOKU) No. 47-40873(1972), Japanese Patent Applications Laid-open (KOKAI) Nos. 50-83497(1975), 50-121336(1975) and 52-155640(1977) or the like.
  • dicarboxylic acid components of polyesters of the primer layers there may be exemplified aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,5-naphthalene dicarboxylic acid or ester-forming derivatives of these acids; aliphatic dicarboxylic acids such as oxy-benzoic acid or ester-forming derivatives thereof; or the like.
  • aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,5-naphthalene dicarboxylic acid or ester-forming derivatives of these acids
  • aliphatic dicarboxylic acids such as oxy-benzoic acid or ester-forming derivatives thereof; or the like.
  • glycol components of polyesters of the primer layers there may be used aliphatic, alicyclic or aromatic diols.
  • diols may include ethylene glycol, 1,4-butane diol, diethylene glycol, triethylene glycol, 1,4-cyclohexane dimethanol, p-xylene diol or the like.
  • poly(oxyalkylene)glycols may be used as the glycol components of the polyesters.
  • examples of the poly(oxyalkylene)glycols may include polyethylene glycol, polypropylene glycol, polytetramethylene. glycol or the like.
  • polyesters of the primer layers there may be used not only saturated linear polyesters composed of the above-mentioned ester-forming components, but also polyesters composed of compounds containing three or less-valent ester-forming components or polyesters having reactive unsaturated groups.
  • water-soluble or water-dispersible polyurethane-based resins used for the production of the primer layer there may be used any known polyurethane-based resins as described in Japanese Patent Publications (KOKOKU) Nos. 42-24194(1967), 46-7720(1971), 46-10193(1971) and 49-37839(1974), Japanese Patent Applications Laid-open (KOKAI) Nos. 50-123197(1975), 53-126058(1978) and 54-138098(1979) or the like.
  • the polyurethane-based resins may comprise as primary polyurethane-constituting components, polyisocyanate, polyol, chain-lengthening agent, cross-linking agent or the like.
  • polyisocyanates may include tolylene diisocyanate, phenylene diisocyanate, 4,4'-diphenylmethane. diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate or the like.
  • polyols may include polyethers such as polyoxyethylene glycol, polyoxypropylene glycol or polyoxytetramethylene glycol; polyesters such as polyethylene adipate, polyethylene-butylene adipate or polycaprolactone; acryl-based polyols; castor oil; or the like.
  • polyethers such as polyoxyethylene glycol, polyoxypropylene glycol or polyoxytetramethylene glycol
  • polyesters such as polyethylene adipate, polyethylene-butylene adipate or polycaprolactone
  • acryl-based polyols such as castor oil; or the like.
  • chain-lengthening agents or cross-linking agents may include ethylene glycol, propylene glycol, butane diol, diethylene glycol, trimethylol propane, hydrazine, ethylene diamine, diethylene triamine, 4,4'-diaminodiphenyl methane, 4,4'-diaminodicyclohexyl methane, water or the like.
  • polyurethane-based resins there may be exemplified those resins having a weight-average molecular weight of 300 to 20,000 and composed of polyols, polyisocyanates, chain-lengthening agents having reactive hydrogen atoms and compounds containing at least one group selected from groups reactive with an isocyanate group, and anionic groups.
  • the anionic groups contained in the polyurethane-based resin may be in the form of lithium salts, sodium salts, potassium salts or magnesium salts of -SO 3 H, -OSO 3 H, -COOH or the like. Among these groups, the sulfonate groups are more preferred.
  • the melamine-based cross-linking agents usable in the primer layer there may be exemplified methoxymethylated melamine or butoxy-methylated melamine which are alkylol-modified or alkoxylol-modified melamine-based compounds. In addition, compounds obtained by co-condensation of a part of melamine with urea or the like may also be used as the melamine-based cross-linking agents.
  • the epoxy-based cross-linking agents usable in the primer layer there may be exemplified compounds containing epoxy groups which are water-soluble or have a percentage of water-solubilization of not less than 50 %.
  • the primer layer can be improved in fixing property, water resistance, solvent resistance and mechanical strength.
  • the adhesion therebetween can be effectively improved.
  • the melamine-based cross-linking agents can show a high curing speed. Therefore, when the melamine-based cross-linking agent is used in combination with a curing catalyst such as proton acids or ammonium salts, the above-mentioned properties can be further enhanced.
  • the amount of the curing (cross-linking) agent used is preferably 0.1 to 60 % by weight based on the weight of a dry solid content of the primer layer.
  • any known coating methods may be used optionally.
  • the suitable coating methods may include a rod coating method, a roll coating method, a gravure coating method, a roll brushing method, a spray coating method, an air-knife' coating method, an immersing method, a curtain coating method or the like. These coating methods may be used solely or in combination.
  • the primer layer may be formed on. either one or both surfaces of the polyester film. It is preferred that the primer layers be formed on both surfaces of the polyester film, because it becomes possible to readily form two top coat layers, i.e., a silicone coat (release layer) on one surface of the film and aback coat layer (rear surface-coating layer) on the other surface thereof.
  • a silicone coat release layer
  • aback coat layer rear surface-coating layer
  • the primer layer may be preferably applied on the fine cell-containing polyester film before completion of its crystal orientation.
  • the fine cell-containing polyester film before completion of its crystal orientation may include an unoriented film obtained by melt-extruding a raw material through an extrusion die on a rotary cooling drum. to form a sheet, and then cooling and solidifying the sheet thereon, a uniaxially oriented film obtained by stretching the unoriented film in either longitudinal or transverse direction, a biaxially oriented film obtained by stretching the uniaxially oriented film in the direction perpendicular to the preceding stretching direction but not subjected to heat fixation for completing the crystal orientation thereof, or the like.
  • the coating solution for the primer layer is applied on the uniaxially oriented film, and dried while the uniaxially oriented film introduced into a tenter is subjected to transverse stretching and heat fixation therein.
  • the solid concentration of the above-mentioned coating solution for the primer layer is usually not more than 30 % by weight, preferably not more than 15 % by weight.
  • the amount of the coating solution applied is preferably 0.5 to 20 g/cm 3 , more preferably 1 to 10 g/cm 3 (calculated as a dry solid content).
  • the coating solution for the primer layer may further contain, if required, various additives such as coating property-modifying agents, thickeners, lubricants, polymer particles, inorganic particles, pigments, dyes, anti-oxidants, ultraviolet-absorbing agents, infrared-absorbing agents, anti-static agents, anti-foaming agents, foaming agents or the like. Since water is used as a solvent of the coating solution, gelatin or an emulsion containing water-soluble resins such as polyvinyl alcohol, vinyl-based resins or epoxy-based resins may be further added to the coating solution, if required.
  • various additives such as coating property-modifying agents, thickeners, lubricants, polymer particles, inorganic particles, pigments, dyes, anti-oxidants, ultraviolet-absorbing agents, infrared-absorbing agents, anti-static agents, anti-foaming agents, foaming agents or the like. Since water is used as a solvent of the coating solution, gelatin or an emulsion containing water-soluble resins such as poly
  • any other known additives such as anti-oxidizing agents, heat stabilizers, anti-static agents, dyes, pigments, surfactants or the like may be blended in polyester and/or polypropylene, if required.
  • an appropriately blended polymer composition is melt-extruded and then stretched in at least one direction by a roll-stretching method, a tentering method or the like.
  • a biaxial stretching method and a heat-treating method' may be usually used in combination.
  • the films produced are in the form of a single layer film which may be made of a single raw material.
  • each molten sheet melt-extruded from the die is rapidly cooled to a temperature below a glass transition temperature thereof on a rotary cooling drum to form a substantially amorphous unoriented sheet.
  • a rotary cooling drum In this case, in order to achieve a high flatness of the sheet and improve the cooling effect, it is preferable to increase the adhesion between the sheet and the rotary cooling drum.
  • an electrostatic pinning method can be suitably used.
  • the thus-obtained unoriented sheet is biaxially stretched to form a biaxially oriented film.
  • Fine cells in the polyester film according to the present invention can be produced by such a stretching method.
  • the unoriented sheet is first stretched in one (longitudinal) direction at a drawing temperature of usually 70 to 150°C, preferably 75 to 130°C and a draw ratio of usually 2.5 to 6.0 times, preferably 3.0 to 5.0 times.
  • a stretching may be conducted by using a roll-type or tenter-type stretching machine.
  • the uniaxially oriented sheet is stretched in the direction perpendicular to the preceding direction (i.e., transverse direction) at a drawing temperature of usually 75 to 150°C, preferably 80 to 140°C and a draw ratio of usually 2.5 to 6.0 times, preferably 3.0 to 5.0 times to obtain a biaxially oriented film.
  • the second stretching may be conducted by using the tenter-type stretching machine.
  • the stretching in each direction can also be conducted in two or more stages. In this case, it is required that the total draw ratio of the sheet is within the above-specified ranges.
  • the afore-mentioned unoriented sheet can be subjected to a simultaneous biaxial stretching such that the surface area draw ratio is 7 to 30 times.
  • the heat treatment of the oriented sheet may be conducted at 150 to 250°C for 1 second to 5 minutes under the condition of an elongation or a limited shrinkage of not more than 30 %, or a constant length.
  • the biaxially oriented film may be re-stretched in the longitudinal (machine) direction at a drawing temperature of 110 to 180°C and a draw ratio of 1.05 to 2.0 times, and thereafter the re-oriented film may be subjected to heat treatment.
  • various procedures such as heat fixation before the longitudinal re-stretching, longitudinal relaxation after the longitudinal re-stretching, or fine longitudinal stretching before or after the longitudinal restretching can be appropriately adopted.
  • the biaxially oriented film can be re-stretched in the transverse direction. Further, the resultant sheet may be subjected to various surface treatments during the film-forming process, if required.
  • the thickness of the thus-produced polyester film according to the present invention is usually 20 to 250 ⁇ m, preferably 37 to 200 ⁇ m, more preferably 40 to 200 ⁇ m.
  • the fine cell-containing polyester film according to the present invention may be suitably applied to image-receiving papers for a printer, mounts for seal print, labels, recording papers, posters, planographic printing plates, wrapping materials, tags or the like.
  • the fine cell-containing polyester film according to the present invention can provide such a polyester film having a specific gloss on opposite surfaces thereof and an image-receiving paper having excellent properties. Therefore, such a fine cell-containing polyester film is extremely useful from the industrial viewpoint.
  • the fine cell-containing polyester film according to the present invention can provide such a polyester film having excellent printability and transport property.
  • the fine cell-containing polyester film according to the present invention can provide a polyester film capable of satisfying both the requirements of adhesion property to a coating layer such as a silicone coat and delivering property upon sheet-feeding (transport property), and can be suitably used as release papers for seal print.
  • part(s) represents “part(s) by weight”, and as a silicone-based surfactant, "SH-193" (produced by TORAY DOW CORNING CO., LTD.) was used.
  • polyester-immiscible polymer components and white pigments were removed, was dissolved in 100 ml of a mixed solvent comprising phenol and tetrachloroethane at weight ratio of 50:50.
  • the intrinsic viscosity of the polyester solution was measured at 30°C.
  • the melt flow index of the polymer was measured at 230°C, 21.1 N according to JIS K-7210-1995.
  • the higher MFI value indicates a lower melt viscosity of the polymer.
  • the particle diameters of the pigment were measured by a centrifugal sedimentation-type particle size distribution measuring apparatus ("SA-CP3 Model", manufactured by SHIMAZU SEISAKUSHO CO., LTD.). The particle diameter of the pigment having a cumulative volume fraction of 50 % in the equivalent spherical distribution was determined as the average particle size of the pigment.
  • the gloss of the surface of the film was measured by controlling a incident angle of light thereon to the MD direction according to Method 3 (60° gloss) of JIS Z-8741-1983.
  • the gloss measurement was conducted three times on each surface of the film. An average of the three measured gloss values was calculated and determined as a gloss of each surface of the film.
  • a square sample having a size of 10 cm x 10 cm was cut from an optional portion of the film.
  • the weight of the sample was measured and the thicknesses thereof were measured by a micrometer at optional 9 points thereof to obtain an average thickness.
  • the weight per unit volume of the sample was calculated from the weight and the average thickness thereof.
  • Five samples (number of measurements: 5) were measured and the average of the measured values was calculated to obtain a film density.
  • the center line average surface roughness (Ra) of the film was measured by a universal surface measuring device ("SE-3E", manufactured by KOSAKA KENKYUSHO CO., LTD.). The measurement was conducted 12 times for one surface (higher-gloss surface) of each sample. The lowermost and uppermost measured values were omitted, and the remaining ten measured values were taken into consideration. The average of the remaining ten measured values' was determined as an average surface roughness (R a ) of the sample.
  • the measuring conditions used were as follows:
  • a visual light was irradiated over the film and an optical density of the film, i.e., an intensity of light transmitted through the film was measured by a Macbeth illuminometer "TD-904 Model". The measurement was conducted five times at the different points thereof and the average of the five measured values was determined as optical density of the film. The larger value of the optical density indicates the lower light transmittance.
  • the brightness of the film was measured by a colorimeter 300A Model (illuminant C, visual field 2°) manufactured by NIHON DENSHOKU KOGYO CO., LTD. according to Method C of JIS L-1015-1981. The measurement was conducted five times at the different points thereof. An average of the measured values on the opposite surfaces of the film was determined as brightness of the film.
  • the casting roll was operated continuously for one hour under the conditions defined in Examples hereinafter. Thereafter, the deposit (soil) on the casting roll was recovered by a feather blade and weighed. The ratios of the weight of the thus recovered soil to that obtained in the preseeding Example 1 are shown in Tables.
  • the film was cut to A4-size sheets.
  • the 30 sheets stacked were set to a manual feed port of a printing machine IMAGIO DA355 manufactured by RICOH CORP. and subjected to printing operations to observe whether or not any double transport thereof was caused.
  • the results were classified into the following ranks:
  • a curable silicone resin (KS-779, produced by SHIN-ETSU KAGAKU KOGYO CO., LTD.), 1 part by weight' of a curing agent (CAT PL-8, produced by SHIN-ETSUKAGAKU KOGYO CO., LTD.) and 2,200 parts by weight of a mixed solvent composed'of methyl ethyl ketone and toluene were mixed together to prepare a coating solution.
  • the coating solution was applied in off-line to a higher-gloss surface of the film by a roll coating method to form thereon a cured silicone resin coating layer having a thickness of 0.1 ⁇ m.
  • the thus obtained film was allowed to stand in a room maintained at 23°C and 50 %RH for 30 days. Thereafter, the coated surface of the film was rubbed with fingers several times to observe falling-off or separation of the cured silicone resin coating layer and evaluate the adhesion property according the following evaluation criteria:
  • the lower-gloss surface of the film was touched with hands.
  • the touch of the film was evaluated according to the following ratings:
  • Crystalline polypropylene chips (13 % by weight) containing 0.25 % by weight of oleamide as a lubricant and having a melt flow index (MFI) of 10 g/10 min, titanium oxide (2.4 % by weight) having an average particle size of 0.3 ⁇ m and the fluorescent brightening agent OB1 (0.05 % by weight) were uniformly blended with polyethylene terephthalate chips (84.55 % by weight) having an intrinsic viscosity of 0.69 to obtain a polyester raw material X.
  • MFI melt flow index
  • the polyester raw material X was charged into an extruder and then melted at 280°C.
  • the thus obtained melt was introduced into a T die and melt-extruded through a slit-like opening on a casting roll maintained at 22°C so that the melt extruded was cooled to form an unoriented sheet.
  • the unoriented sheet was roll-stretched in the machine (longitudinal) direction at a drawing temperature of 83°C and a draw ratio of 3.2 times.
  • the uniaxially oriented sheet was introduced into a tenter-type stretching machine, stretched in the transverse direction at a drawing temperature of 115°C and a draw ratio of 3.2 times and then heat-treated in the stretching machine-at 230°C for 5 seconds, thereby obtaining a biaxially oriented fine cell-containing film having a thickness of 50 ⁇ m.
  • Example 2 The same procedure as defined in Example 1 was conducted except that crystalline polypropylene chips containing 0.015 % by weight of erucamide as a lubricant and having a melt flow index (MFI) of 10 g/10 min were used instead of those used in Example 1, thereby obtaining a biaxially oriented fine cell-containing film.
  • MFI melt flow index
  • Example 2 The same procedure as defined in Example 1 was conducted except that crystalline polypropylene chips containing 0.25 % by weight of stearamide as a lubricant and having a melt flow index (MFI) of 10 g/10 min were used instead of those used in Example 1, thereby obtaining a biaxially oriented fine cell-containing film.
  • MFI melt flow index
  • Example 1 Example 2
  • Example 3 Gloss Cast surface 38.6 34.3 28.5 Air-side surface 25.6 25.8 25.0 Difference between the opposite surfaces 13.0 8.5 3.5
  • Film density 1.01 1.00 1.00
  • Optical density 0.51 0.51 0.53
  • Brightness (W value) 82.0 82.4 79.2
  • Intrinsic viscosity (IV) of film 0.60 0.62 0.58 Definition or clarity of printed image o ⁇ o ⁇ ⁇ Amount of deposit (soil) on casting roll 1.0 6.2 10
  • the dehydrated mixture was maintained at 70°C and mixed with a mixture containing 178 parts of isophorone diisocyanate and 244 parts of hexamthylene-1,6-diisocyanate. Next, the resultant mixture was stirred at a temperature of 80 to 90°C until the isocyanate content reached 5.6 % by weight, thereby obtaining a prepolymer.
  • Crystalline polypropylene chips (13 % by weight) having a melt flow index (MFI) of 10 g/10 min, titanium oxide (2.5 % by weight) having an average particle size of 0.3 ⁇ m, the fluorescent brightening agent OB1 (0.05 % by weight) and a silicone-based surfactant (0.1 % by weight) were uniformly blended with polyethylene terephthalate chips (84.35 % by weight) having an intrinsic viscosity of 0.69 to obtain a polyester raw material X1.
  • MFI melt flow index
  • the polyester raw material X1 was charged into an extruder and then melted at 280°C.
  • the thus obtained melt was introduced into a T die and melt-extruded through a slit-like opening on a casting roll maintained at 30°C, so that the melt extruded was cooled to form an unoriented sheet.
  • the unoriented sheet was roll-stretched in the machine (longitudinal) direction at a drawing temperature of 82°C and a draw ratio of 3.25 times. Further, the coating solution was applied to opposite surfaces of the obtained uniaxially oriented sheet to form primer layers each having thickness of 5 ⁇ m.
  • the coated sheet was introduced into a tenter-type stretching machine, stretched in the transverse direction at a drawing temperature of 125°C and a draw ratio of 3.8 times and then heat-treated in the tenter-type stretching machine at 230°C for 5 seconds to obtain a biaxially oriented fine cell-containing film having a thickness of 100 ⁇ m.
  • the thus-obtained film was excellent in adhesion to the silicone coat and transport property in a copying machine.
  • Reference Examples 4 and 5 are shown in Table 2.
  • Reference Example 4 Reference Example 5 Gloss Higher-gloss surface 37.1 53.6 Lower-gloss surface 24.1 31.4 Film density 1.02 1.03 Surface roughness Ra ( ⁇ m) 0.17 0.16 Optical density 0.89 0.88 Brightness (W value) 87.7 88.1 Intrinsic viscosity (IV) of film 0.61 0.60 Transport property in printer ⁇ ⁇ Adhesion to silicon coat ⁇ ⁇ Touch of film ⁇ ⁇
  • Crystalline polypropylene chips (13 % by weight) containing 1.0 % by weight of a silicone-based surfactant composed of polydimethylsiloxane-polyoxyalkylene copolymer (SH193, produced by TORAY DOW CORNING CO., LTD.) and having a melt flow index (MFI) of 10 g/10 min, titanium oxide (2.4 % by weight) having an average particle size of 0.3 ⁇ m and the fluorescent brightening agent OB1 (0.05 % by weight) were uniformly blended with polyethylene terephthalate chips (84.55 % by weight) having an intrinsic viscosity of 0.69 to obtain a polyester raw material X2.
  • a silicone-based surfactant composed of polydimethylsiloxane-polyoxyalkylene copolymer (SH193, produced by TORAY DOW CORNING CO., LTD.) and having a melt flow index (MFI) of 10 g/10 min, titanium oxide (2.4 % by weight) having an average particle size
  • the obtained polyester raw material X2 was charged into an extruder and then melted at 280°C.
  • the thus obtained melt was introduced into a T die and melt-extruded through a slit-like opening on a casting roll maintained at 22°C, so that the melt extruded was cooled to form an unoriented sheet.
  • the unoriented sheet was roll-stretched in the machine (longitudinal) direction at a drawing temperature of 83°C and a draw ratio of 3.4 times.
  • the uniaxially oriented sheet was introduced into a tenter-type stretching machine, stretched in the transverse direction at a drawing temperature of 115°C and a draw ratio of 3.0 times and then heat-treated in the tenter-type stretching machine at 230°C for 5 seconds to obtain a biaxially oriented fine cell-containing film having a thickness of 50 ⁇ m.
  • Reference Examples 6 to 8 are shown in Table 3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Claims (21)

  1. Film de polyester à fines alvéoles comprenant de 70 à 97 % en poids d'un polyester, et de 3 à 30 % en poids d'une résine thermoplastique non miscible au polyester, et produit par étirage selon au moins une direction,
       dans lequel ladite résine thermoplastique non miscible au polyester contient au moins un amide d'acide gras ne comportant pas moins de 10 atomes de carbone ou un lubrifiant, et
       la différence de brillance entre les surface opposées dudit film de polyester n'étant pas inférieure à 3 %, et la brillance d'une surface dudit film de polyester n'étant pas inférieure à 25 %, la brillance étant mesurée selon le procédé 3 de la norme JIS Z 8741-1983 (brillance à 60°).
  2. Film de polyester à fines alvéoles selon la revendication 1, dans lequel une surface dudit film de polyester a une brillance Gc non inférieure à 33 %, et l'autre surface dudit film de polyester a une brillance Ga de 25 ± 7 %.
  3. Film de polyester à fines alvéoles selon la revendication 1, dans lequel la surface dont la brillance n'est pas inférieure à 25 %, a une rugosité superficielle Ra de 0,06 à 0,25 µm.
  4. Film de polyester à fines alvéoles selon la revendication 1, dans lequel la teneur en ledit lubrifiant dans la résine thermoplastique est de 0,005 à 2,0 % en poids par rapport au poids total du lubrifiant et de la résine thermoplastique.
  5. Film de polyester à fines alvéoles selon la revendication 1, dans lequel la résine thermoplastique non miscible au polyester, est le polypropylène.
  6. Film de polyester à fines alvéoles selon la revendication 5, dans lequel ledit polypropylène a un indice de fluidité à chaud de 0,5 à 30 g/10 min.
  7. Film de polyester à fines alvéoles selon la revendication 1, ayant en outre une masse volumique de 0,70 à 1,30 g/cm3.
  8. Film de polyester à fines alvéoles selon la revendication 1, dans lequel la différence de brillance entre lesdites faces opposées dudit film de polyester, n'est pas inférieure à 10 %.
  9. Film de polyester à fines alvéoles selon la revendication 1, dans lequel la surface dudit film de polyester a une brillance non inférieure à 35 %.
  10. Film de polyester à fines alvéoles selon la revendication 2, comprenant en outre une couche primaire sur les deux surfaces dudit film de polyester.
  11. Film de polyester à fines alvéoles selon la revendication 10, dans lequel ladite couche primaire comprend une résine à base de polyester soluble dans l'eau ou une résine à base de polyester dispersible dans l'eau.
  12. Film de polyester à fines alvéoles selon la revendication 2, dans lequel la brillance Gc d'une de ses surfaces, est de 33 à 47 %, et la brillance Ga de l'autre de ses surfaces est de 20 à 30 %.
  13. Film de polyester à fines alvéoles selon la revendication 2, dans lequel la teneur de ladite résine thermoplastique est de 8 à 25 % en poids par rapport au poids du film de polyester à fines alvéoles.
  14. Film de polyester à fines alvéoles selon la revendication 3, dans lequel la résine thermoplastique non miscible avec ledit polyester, contient un tensioactif non ionique.
  15. Film de polyester à fines alvéoles selon la revendication 14, dans lequel ledit tensioactif non ionique est un tensioactif à base de silicone.
  16. Film de polyester à fines alvéoles selon la revendication 14, dans lequel la teneur en ledit tensioactif non ionique dans la résine thermoplastique est de 0,01 à 10 % en poids par rapport au poids total du tensioactif non ionique et de la résine thermoplastique.
  17. Film de polyester à fines alvéoles selon la revendication 16, dans lequel la teneur en ledit tensioactif non ionique dans la résine thermoplastique, est de 0,2 à 5,0 % en poids par rapport au poids total du tensioactif non ionique et de la résine thermoplastique.
  18. Film de polyester à fines alvéoles selon la revendication 3, dans lequel ladite rugosité superficielle Ra de la surface dont la brillance n'est pas inférieure à 25 %, est de 0,08 à 0,20 µm.
  19. Papier récepteur d'image pour imprimante vidéo, comprenant :
    le film de polyester à fines alvéoles tel que défini dans la revendication 1 ; et
    une couche d'enregistrement photosensible formée sur la surface dont la brillance n'est pas inférieure à 25 %.
  20. Papier récepteur d'image pour imprimante vidéo, comprenant :
    le film de polyester à fines alvéoles tel que défini dans la revendication 14 ; et
    une couche d'enregistrement photosensible formée sur la surface dont la brillance n'est pas inférieure à 25 %.
  21. Papier anti-adhérent pour épreuve scellée, comprenant le film de polyester à fines alvéoles tel que défini dans la revendication 2.
EP98114927A 1997-08-12 1998-08-07 Pellicule en polyester contenant des cellules infimes Expired - Lifetime EP0897947B2 (fr)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
JP21740897 1997-08-12
JP21740997 1997-08-12
JP21740897A JP3982774B2 (ja) 1997-08-12 1997-08-12 微細気泡含有ポリエステルフィルムおよび当該フィルムからなるビデオプリンター用受像紙
JP9217409A JPH1160766A (ja) 1997-08-12 1997-08-12 微細気泡含有ポリエステルフィルムおよびシールプリント用離型紙
JP217409/97 1997-08-12
JP217408/97 1997-08-12
JP294034/97 1997-10-27
JP29403497 1997-10-27
JP9294034A JPH11130887A (ja) 1997-10-27 1997-10-27 微細気泡含有ポリエステルフィルムおよびビデオプリンター用受像紙
JP33151197 1997-12-02
JP9331511A JPH11157037A (ja) 1997-12-02 1997-12-02 微細気泡含有積層ポリエステルフィルムおよびビデオプリンター用受像紙
JP331511/97 1997-12-02

Publications (4)

Publication Number Publication Date
EP0897947A2 EP0897947A2 (fr) 1999-02-24
EP0897947A3 EP0897947A3 (fr) 1999-08-25
EP0897947B1 EP0897947B1 (fr) 2002-03-27
EP0897947B2 true EP0897947B2 (fr) 2005-12-28

Family

ID=27476825

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98114927A Expired - Lifetime EP0897947B2 (fr) 1997-08-12 1998-08-07 Pellicule en polyester contenant des cellules infimes

Country Status (3)

Country Link
US (1) US6130278A (fr)
EP (1) EP0897947B2 (fr)
DE (1) DE69804392T3 (fr)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE60036749T2 (de) * 1999-05-12 2008-08-28 Mitsubishi Polyester Film Corp. Mikrozelluläre Polyesterfolie
WO2001040361A1 (fr) * 1999-12-01 2001-06-07 Yupo Corporation Film en resine poreuse
AU1731701A (en) * 1999-12-07 2001-06-18 Oji-Yuka Synthetic Paper Co., Ltd. Porous resin film
WO2001062843A2 (fr) * 2000-02-23 2001-08-30 Lumin-Oz, Llc Feuille extrudee a brillant de surface controlee et procede de fabrication associe
DE10051083A1 (de) * 2000-10-14 2002-04-25 Mitsubishi Polyester Film Gmbh Koextrudierte, zumindest einseitig matte, biaxial orientierte Polyesterfolie
DE10051084A1 (de) * 2000-10-14 2002-04-25 Mitsubishi Polyester Film Gmbh Matte, biaxial orientierte Polyesterfolie
WO2002085622A1 (fr) † 2001-04-19 2002-10-31 Toray Industries, Inc. Film polyester stratifie blanc et feuille de reception pour enregistrement par transfert thermique par it
JP5239448B2 (ja) * 2007-06-04 2013-07-17 東レ株式会社 帯電防止性白色ポリエステルフィルム
WO2009058821A1 (fr) * 2007-10-31 2009-05-07 Dupont Teijin Films U.S. Limited Partnership Articles revêtus
KR100995514B1 (ko) * 2007-12-21 2010-11-19 (주)엘지하우시스 기록용 원단 및 그 제조방법
CN103991258B (zh) * 2009-03-31 2015-09-23 帝人杜邦薄膜日本有限公司 太阳能电池背面保护膜用层压聚酯膜
US8721152B2 (en) * 2009-05-01 2014-05-13 Abl Ip Holding Llc Light emitting devices and applications thereof
JP5799806B2 (ja) * 2010-04-27 2015-10-28 東レ株式会社 積層フィルムおよび成型体
JP7264294B2 (ja) * 2017-03-02 2023-04-25 三菱ケミカル株式会社 積層白色フィルムおよび被記録材
KR102601068B1 (ko) 2017-03-02 2023-11-13 미쯔비시 케미컬 주식회사 적층 백색 필름 및 피기록재
JP7264295B2 (ja) * 2017-03-02 2023-04-25 三菱ケミカル株式会社 積層白色ポリエステルフィルムおよび被記録材
JP7052306B2 (ja) * 2017-03-02 2022-04-12 三菱ケミカル株式会社 積層白色フィルムおよび被記録材
JP7052307B2 (ja) * 2017-03-02 2022-04-12 三菱ケミカル株式会社 積層白色ポリエステルフィルムおよび被記録材
CN109851919A (zh) * 2019-01-30 2019-06-07 铜陵鸿盛百诚新能源科技有限公司 一种防潮抗氧化智能光伏用金属化安全膜及其制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63168441A (ja) * 1986-12-27 1988-07-12 Diafoil Co Ltd 微細気泡含有ポリエステルフイルム
JPH0717777B2 (ja) * 1987-02-05 1995-03-01 ダイアホイルヘキスト株式会社 微細気泡含有ポリエステルフイルム
US4857396A (en) * 1987-02-05 1989-08-15 Daifoil Company, Ltd. Minute-cellular polyester film provided with coating
JPH0622962B2 (ja) * 1988-09-19 1994-03-30 ダイアホイルヘキスト株式会社 積層フィルム
JP2893286B2 (ja) * 1990-05-17 1999-05-17 グンゼ株式会社 熱収縮性発泡複合フィルム及びその製法
US5422175A (en) * 1992-06-01 1995-06-06 Toyo Boseki Kabushiki Kaisha Void-containing composite film of polyester type
JPH06307705A (ja) * 1993-04-20 1994-11-01 Toshiba Corp 空気調和機の湿度制御方法
DE19540277B4 (de) * 1994-11-02 2007-04-19 Toyo Boseki K.K. Folie mit feinen Hohlräumen und Verfahren zu deren Herstellung
US6004664A (en) * 1994-11-02 1999-12-21 Toyo Boseki Kabushiki Kaisha Film having fine voids and manufacture thereof

Also Published As

Publication number Publication date
DE69804392T2 (de) 2002-11-28
EP0897947A3 (fr) 1999-08-25
DE69804392D1 (de) 2002-05-02
EP0897947A2 (fr) 1999-02-24
DE69804392T3 (de) 2006-08-31
EP0897947B1 (fr) 2002-03-27
US6130278A (en) 2000-10-10

Similar Documents

Publication Publication Date Title
EP0897947B2 (fr) Pellicule en polyester contenant des cellules infimes
EP0911152B1 (fr) Film polyester blanc stratifié et support de formation d'image
EP1110716A2 (fr) Film multicouche en polyester
US6136420A (en) Laminated polyester film
JP4441838B2 (ja) 空洞含有複合ポリエステル系フィルム及び感熱転写記録材料用基材フィルム
JP3731720B2 (ja) 空洞含有ポリエステル系フィルム
JP3622860B2 (ja) 配送伝票用ポリエステル系フィルム
JPH11157037A (ja) 微細気泡含有積層ポリエステルフィルムおよびビデオプリンター用受像紙
EP0835752A2 (fr) Feuille en polyester stratifié et feuille pour impression par jet d'encre
JP3021519B2 (ja) 印刷用受容シート
JP3326033B2 (ja) 印画紙用微細気泡含有積層ポリエステルフィルム
JP3636346B2 (ja) 空洞含有ポリエステル系フィルム
JP4131452B2 (ja) 空洞含有ポリエステル系フィルム
JP2733974B2 (ja) プリンター用感熱転写材
JP2001049001A (ja) 微細気泡含有ポリエステルフィルム
JPH09239883A (ja) 微細気泡含有積層ポリエステルフイルム及び当該フイルムから成るカラープリンター用受像紙
JP4286937B2 (ja) 微細気泡含有積層ポリエステルフィルムおよびラミネート金属缶
JP2005007787A (ja) 熱転写リボン用ポリエステルフィルム
JPH1160766A (ja) 微細気泡含有ポリエステルフィルムおよびシールプリント用離型紙
JP2006028523A (ja) 空洞含有ポリエステル系フィルム
JP2001200075A (ja) 再生フィルム
JPH07216121A (ja) 配送伝票用ポリエステル系フィルム
JP2000318079A (ja) 多層延伸フィルム及び延伸ポリエチレン−２，６−ナフタレートフィルム
JPH08216346A (ja) 積層フイルム
JPH0939140A (ja) 写真印画用空洞含有ポリエステル系フィルム

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE FR GB IT LU NL

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 19990924

AKX Designation fees paid

Free format text: DE FR GB IT LU NL

17Q First examination report despatched

Effective date: 20010207

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT LU NL

REF Corresponds to:

Ref document number: 69804392

Country of ref document: DE

Date of ref document: 20020502

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: TORAY INDUSTRIES, INC.

Effective date: 20021227

NLR1 Nl: opposition has been filed with the epo

Opponent name: TORAY INDUSTRIES, INC.

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20040806

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20040831

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050807

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050807

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20051228

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): DE FR GB IT LU NL

NLR2 Nl: decision of opposition

Effective date: 20051228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060301

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20060301

ET3 Fr: translation filed ** decision concerning opposition
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20130821

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20130821

Year of fee payment: 16

Ref country code: FR

Payment date: 20130823

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69804392

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20140807

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69804392

Country of ref document: DE

Effective date: 20150303

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20150430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140807

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150303

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140901